CN110975928B - Modification method and application of binder-free ZSM-11 molecular sieve catalyst - Google Patents
Modification method and application of binder-free ZSM-11 molecular sieve catalyst Download PDFInfo
- Publication number
- CN110975928B CN110975928B CN201911238292.1A CN201911238292A CN110975928B CN 110975928 B CN110975928 B CN 110975928B CN 201911238292 A CN201911238292 A CN 201911238292A CN 110975928 B CN110975928 B CN 110975928B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sieve catalyst
- zsm
- catalyst
- binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a production technology of petrochemical products, in particular to a modification method and application of a binder-free ZSM-11 molecular sieve catalyst. A modification method and application of a binder-free ZSM-11 molecular sieve catalyst are disclosed, the preparation method comprises the following specific steps: exchanging the prepared ZSM-11 molecular sieve catalyst without the binding agent with an ammonium nitrate solution, drying and roasting to prepare an H-molecular sieve catalyst; rare earth nitrate and aluminum salt are adopted to load rare earth and aluminum on the H-molecular sieve catalyst by a conventional impregnation method, and the required catalyst is prepared by steam treatment, acidification and roasting. The catalyst prepared by the invention is applied to the preparation of ethylene and propylene by catalytic cracking of carbon tetraolefin. The invention has the advantages that: according to the method, the catalyst obtained by acidification is good in stability and the catalytic efficiency is improved in the process of converting the carbon tetraolefin into the ethylene and the propylene through catalytic cracking.
Description
Technical Field
The invention relates to a production technology of petrochemical products, in particular to a modification method and application of a binder-free ZSM-11 molecular sieve catalyst.
Background
Ethylene and propylene are important organic chemical raw materials, and the demand for the ethylene and the propylene is increasing along with the rapid development of national economy. In addition to hydrocarbon steam cracking, catalytic cracking and methanol-to-olefins, catalytic cracking of carbon tetraolefins is also one of the important ways to obtain ethylene and propylene. The technology has the characteristics of simple process, less investment and quick response, and is favored by the industrial and academic circles.
Patents CN1611471A and CN1611472A propose a method for producing propylene by catalytic cracking of olefin, in which the former uses a phosphorus-modified ZSM-5 molecular sieve catalyst with a low silica-alumina ratio to improve the selectivity and yield of the target product propylene. The catalyst is a ZSM-5 type molecular sieve with the preferred range of the silica-alumina ratio of 230 to 600, and the residence time of reactants and products is reduced by regulating the grain size of the ZSM5 type molecular sieve so as to achieve the purpose of improving the selectivity and the stability of the catalyst. The patent focuses on the synthesis of the molecular sieve raw powder, and other active components are not added for modification.
The patent CN1600757 adopts ZSM-5/ZSM-11 cocrystallized molecular sieve after ammonium ion exchange, uses K, mg, la and Ce to adjust the performance of the molecular sieve, uses butylene as raw material, and adopts liquid phase space velocity at 500-600 ℃ and1~50 h-1and under the condition of 0.01 to 0.8 MPa, the total yield of the ethylene and the propylene reaches 40 to 50 percent. The catalytic cracking reaction time is short, and the stability of the catalyst is not investigated.
In patent CN1490288, halogen sodium salt is added in the crystallization process of ZSM type molecular sieve raw powder, and olefins with four carbon atoms and above four carbon atoms are used as reaction raw materials, so that the influence of different ratios of halogen sodium salt and silicon dioxide on catalytic cracking reaction in the crystallization process of the molecular sieve is examined in detail, the crystallization synthesis of the molecular sieve is emphasized, and the selectivity and stability of propylene in the reaction process are not further described.
CN1274342A discloses a process for the preparation of ethylene and propylene by converting a straight-chain hydrocarbon containing 20 wt.% or more (based on the weight of the hydrocarbon feedstock) of at least one C4-C12 olefin as feedstock. The zeolite in the zeolite catalyst used in the process is SiO2/Al2O3The molecular ratio is 200-5000, the zeolite contains at least one IB group metal, the zeolite with medium aperture is preferably ZSM-5 family zeolite, the reaction is carried out at 400-700 ℃, the pressure is 0.1-10 atmospheric pressure and the reaction time is 1-1000 h-1With the use of diluent gases comprising hydrogen, methane, steam and inert gases, yields of ethylene up to 6.5% and yields of propylene of 22.7% were obtained without further elucidation of the stability.
CN1313268A discloses a method for preparing ethylene by taking C2-C5 gaseous hydrocarbons, such as natural gas, liquefied gas or catalytic cracking gas, as raw materials. In the method, a layered clay-containing molecular sieve catalyst is used at the temperature of 650-750 ℃ and the temperature of 1.5x105 ~ 4x105Pa, reaction time 0.2-1 second, ethylene yield up to 15.49% and propylene yield of 25.19% can be obtained, without further elaboration on stability.
WO 00/26163 discloses a process for the preparation of ethylene and propylene starting from a mixture comprising C4 and C5 olefins in the presence of a zeolite catalyst. The catalyst used in the method is zeolite with the pore diameter of more than 3.5 angstroms, one-dimensional non-interconnected pore canals and the pore volume of 14 to 28, and the reaction is carried out at the temperature of 200 to 700 ℃, the atmospheric pressure of 0.5 to 10 and the time of 0.5 to 1000 h-1At a weight hourly space velocity of (a) without the addition of other active ingredientsAnd (5) modifying.
CN101927180 discloses a catalyst for preparing propylene from carbon tetraenes, which comprises 75-95% of high-silicon zeolite (ZRP or ZSM-5), 5-20% of silicon oxide and 1-10% of a modifying component (calcium oxide and/or lithium oxide, boron oxide or phosphorus oxide). The catalyst has good stability and regeneration performance.
Kingwenqing et al [ chemical reaction engineering and process, 2007, 23 (3): 193-199] studied the performance of catalytic cracking of butene on ZSM-5 molecular sieve after sodium hydroxide treatment to produce ethylene and propylene, and the results show that the mesopores introduced after alkali treatment can promote the catalytic cracking of butene to produce ethylene and propylene.
Zhao nationality et al (catalytic science, 2005, 26 (12): 1083-1087) have investigated the cracking performance of butene on the molecular sieve catalyst after modification of ammonium fluorosilicate, find that ammonium fluorosilicate can reduce the surface acidity of the molecular sieve, inhibit hydrogen transfer and aromatization side reaction to a certain extent; the pore channels of the molecular sieve are dredged, and the stability of the catalyst is improved.
CN108689788A discloses a method for preparing propylene by catalytic cracking of carbon tetraolefin, wherein the active component of the catalyst is a deactivated titanium-containing molecular sieve with MFI structure or a mixture of the deactivated titanium-containing molecular sieve with MFI structure and a phosphorus-modified ZSM-5 molecular sieve.
Wutao et al reported that [ Fuel Pr ℃ evolving Technology, 2018, 173.
The fine molecular sieve powder can not meet the requirements of practical application, and in order to ensure that molecular sieve catalysts in different shapes have corresponding mechanical strength, the binder is an indispensable forming aid. At present, the adhesive mainly adopts silicon oxide and aluminum oxide, wherein aluminum atoms in the aluminum oxide adhesive enter a molecular sieve framework to increase the acid content of the molecular sieve; the silica binder reduces the acid content and decreases the strength. If the silicon oxide adhesive is converted into molecular sieve, it can be formed into catalytic material with a certain shape, size and mechanical strength together with original molecular sieve, i.e. adhesive-free molecular sieve catalyst, and can fully exert the reaction performance of catalyst under the condition of ensuring the mechanical strength and acid quantity of catalyst.
Catalytic cracking of carbon tetraolefins is one of the important routes to ethylene and propylene. In 2014, we applied for a binderless ZSM-11 molecular sieve catalyst (CN 105728017A, granted in 2018), and on the basis, applied for a patent of carbon four-olefin catalytic cracking reaction on the modified binderless ZSM-11 molecular sieve catalyst. The rare earth or aluminum is singly used for modification on the non-adhesive, the stability of the catalyst is improved to a certain extent, the stability of the catalyst can be obviously improved after combination (see comparative examples 1,2 and 3 and example 1), and the micro-mesoporous structure of the catalyst and the acidity in the catalyst can be regulated and controlled after the rare earth and the aluminum are jointly modified.
Disclosure of Invention
Compared with the catalyst containing only the ZSM-11 molecular sieve without the binder, the catalyst provided by the invention can be used for catalytically cracking and converting carbon tetraolefin into ethylene and propylene, and simultaneously improving the stability of the catalyst.
The invention provides a modification method of a binder-free ZSM-11 molecular sieve catalyst, which comprises the following specific steps:
(1) Roasting the prepared binder-free ZSM-11 molecular sieve catalyst (CN 105728017A) at 500-550 ℃ for 3-5H to burn out a template agent, exchanging the template agent with 0.6-0.8 mol/L ammonium nitrate solution at 60-80 ℃, drying, and roasting at 500-550 ℃ for 3-5H to prepare the H-type molecular sieve;
(2) Loading rare earth and aluminum on the product obtained in the step (1) by a conventional impregnation method, wherein the loading amount of the rare earth is 0.1-6.0 wt% (preferably 1.0-3.0 wt%), the loading amount of the aluminum is 0.5-5.0 wt%, drying at 80-100 ℃ for 1-3 h, and roasting at 500-600 ℃ in an air atmosphere for 3-6 h;
(3) Treating the product obtained in the step (2) at 550-750 ℃ for 3-15 h (preferably 4-8 h) in a steam atmosphere, and then acidifying and roasting to obtain the required catalyst; the acidification temperature is 60 to 80 ℃, and the acidification time is 2 hours.
Further, in the step (3), acidification is achieved by oxalic acid.
Preferably, in the step (1), the concentration of the ammonium nitrate solution is 0.6-0.8 mol/L; the temperature of the exchange is 60-80 ℃.
Preferably, in the step (1), the roasting temperature is 550-750 ℃, and the roasting time is 3-15 h.
Preferably, in the rare earth-AlZSM-11 in the step (2), the loading amount of the rare earth is 0.1-6.0 wt%, and the loading amount of the aluminum is 0.5-5.0 wt%.
Furthermore, the loading amount of the rare earth is 1.0-3.0 wt%.
Preferably, in the step (2), the drying temperature is 80-100 ℃, and the drying time is 1-3 h; the roasting temperature is 550-700 ℃, and the roasting time is 3-6 h.
Preferably, in the step (3), the temperature of the steam treatment is 550-750 ℃ and the time is 1-8 h.
Further, in the step (3), the water vapor treatment time is 3-5 h.
In summary, the catalyst provided by the invention is prepared by subjecting binder-free ZSM-11 molecular sieve catalyst to ammonium exchange, drying, roasting to obtain H-type molecular sieve, then conventionally impregnating and loading rare earth and aluminum, performing steam treatment, acidifying and roasting to obtain the required catalyst.
The invention has the beneficial effects that:
according to the method, the catalyst is obtained through acidification, and the stability of the catalyst is good in the process of converting the carbon tetraolefin into ethylene and propylene through catalytic cracking, so that the catalytic efficiency is improved.
Drawings
FIG. 1 is a graph comparing the effects of the examples of the present invention.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Comparative example 1
10 g of ZSM11 molecular sieve is weighed, 6.25 g of 40% (weight) silica sol is added and mixed, extrusion molding is carried out, and the sample A is obtained after drying at 120 ℃. A mixture of 5 g of tetrabutylammonium bromide, 10 g of 1, 6-hexamethylenediamine and 30 g of distilled water is added in advance to a reaction kettle, 10 g of the sample A is placed in the reaction kettle above a porous stainless steel net for sealing, and then gas-solid phase treatment is carried out for 14 hours at 180 ℃ to obtain a binderless product B (the sum of the intensities of diffraction peaks characteristic to the XRD spectrum of the sample A is defined as 100%, and the relative crystallinity obtained by the ratio of the product B to the product A is 138%).
And taking out the product B, washing with distilled water, drying, roasting at 750 ℃ for 6H, exchanging with 0.6 mol/L ammonium nitrate solution at 60 ℃ for 3 times, washing with water for 2 times, drying at 120 ℃, roasting at 550 ℃ for 3H to obtain an H-type molecular sieve, treating with water vapor at 550 ℃ for 5H, and roasting at 540 ℃ for 2H to obtain the catalyst named Cat-A.
Comparative example 2
In comparative example 1, the product B without the binder is washed by distilled water, dried, roasted at 550 ℃ for 4H, exchanged by 0.8 mol/L ammonium nitrate solution at 80 ℃ for 3 times, washed by water for 2 times, dried at 120 ℃ and roasted at 540 ℃ for 3H to obtain an H-type molecular sieve, then the loaded rare earth is impregnated conventionally, lanthanum nitrate solution is adopted, dried at 85 ℃ for 2H and roasted at 550 ℃ for 4H to obtain the catalyst La with the loading of 2.5wt%, then the catalyst La is treated by water vapor at 600 ℃ for 5H and roasted at 540 ℃ for 2H, and the obtained catalyst is recorded as Cat-B.
Comparative example 3
In comparative example 1, the binderless product B was washed with distilled water, dried, calcined at 550 ℃ for 4 hours, exchanged with 0.8 mol/L ammonium nitrate solution at 80 ℃ for 3 times, washed with water for 2 times, dried at 120 ℃ and calcined at 540 ℃ for 3 hours to obtain an H-type molecular sieve, then the supported aluminum was impregnated conventionally, dried with aluminum nitrate solution at 85 ℃ for 2 hours and calcined at 550 ℃ for 4 hours to obtain a supported amount of Al catalyst of 4.0 wt%, then treated with steam at 600 ℃ for 5 hours and calcined at 540 ℃ for 2 hours, and the obtained catalyst was denoted as Cat-C.
Comparative example 4
In comparative example 1, the binder-free product B was washed with distilled water, dried, calcined at 550 ℃ for 4 hours, exchanged with 0.8 mol/L ammonium nitrate solution at 80 ℃ for 3 times, washed with water for 2 times, dried at 120 ℃ and calcined at 540 ℃ for 3 hours to obtain an H-type molecular sieve, then the supported rare earth and aluminum were impregnated conventionally, dried at 85 ℃ for 2 hours and calcined at 550 ℃ for 4 hours using lanthanum nitrate and aluminum nitrate solutions, and the obtained supported amounts of La and Al were 2.5wt% and 4.0 wt%, respectively, followed by steam treatment at 600 ℃ for 5 hours and calcination at 540 ℃ for 2 hours, and the obtained catalyst was denoted as Cat-D.
Example 1
In comparative example 1, the product B without the binder is washed with distilled water, dried, roasted at 750 ℃ for 6H, exchanged with 0.6 mol/L ammonium nitrate solution at 60 ℃ for 3 times, washed with water for 2 times, dried at 120 ℃, roasted at 550 ℃ for 3H to obtain an H-type molecular sieve, treated with water vapor at 550 ℃ for 5H, acidified with oxalic acid at 70 ℃ for 2H, and roasted at 540 ℃ for 2H, and the obtained catalyst is marked as Cat-E.
Example 2
In comparative example 1, the product B without the binder is washed by distilled water, dried, roasted at 550 ℃ for 4H, exchanged by 0.8 mol/L ammonium nitrate solution at 80 ℃ for 3 times, washed by water for 2 times, dried at 120 ℃, roasted at 540 ℃ for 3H to obtain the H-type molecular sieve, then the loaded rare earth is impregnated conventionally, lanthanum nitrate solution is adopted, dried at 85 ℃ for 2H, and roasted at 550 ℃ for 4H to obtain the catalyst La with the loading of 2.5wt%, then treated by water vapor at 600 ℃ for 5H, acidified by 70 ℃ with oxalic acid for 2h, and roasted at 540 ℃ for 2H, and the obtained catalyst is recorded as Cat-F.
Example 3
In comparative example 1, the product B without the binder is washed by distilled water, dried, roasted at 550 ℃ for 4H, exchanged by 0.8 mol/L ammonium nitrate solution at 80 ℃ for 3 times, washed by water for 2 times, dried at 120 ℃, roasted at 540 ℃ for 3H to obtain an H-type molecular sieve, then the supported aluminum is impregnated conventionally, the supported aluminum is dried by using aluminum nitrate solution at 85 ℃ for 2H and roasted at 550 ℃ for 4H to obtain the catalyst Al with the supported amount of 4.0 wt%, then treated by water vapor at 600 ℃ for 5H and acidified by 70 ℃ oxalic acid for 2H, and roasted at 540 ℃ for 2H, and the obtained catalyst is marked as Cat-G.
Example 4
In comparative example 1, the product B without the binder is washed by distilled water, dried, roasted at 550 ℃ for 4H, exchanged by 0.8 mol/L ammonium nitrate solution at 80 ℃ for 3 times, washed by water for 2 times, dried at 120 ℃ and roasted at 540 ℃ for 3H to obtain the H-type molecular sieve, then the loaded rare earth and aluminum are impregnated conventionally, lanthanum nitrate and aluminum nitrate solution is adopted, dried at 85 ℃ for 2H and roasted at 550 ℃ for 4H, the loaded amount of the obtained catalysts La and Al are 2.5wt% and 4.0 wt% respectively, then the catalysts La and Al are treated by water vapor at 600 ℃ for 5H and oxalic acid at 70 ℃ for 2h, and roasted at 540 ℃ for 2H, and the obtained catalyst is marked as Cat-H.
Example 5
In comparative example 1, the binder-free product B was washed with distilled water, dried, calcined at 550 ℃ for 4 hours, exchanged with 0.8 mol/L ammonium nitrate solution at 80 ℃ for 3 times, washed with water for 2 times, dried at 120 ℃ and calcined at 540 ℃ for 3 hours to obtain an H-type molecular sieve, then the supported rare earth and aluminum were impregnated conventionally, dried at 85 ℃ for 2 hours and calcined at 550 ℃ for 4 hours using lanthanum nitrate and aluminum nitrate solutions, and the obtained supported amounts of La and Al were 2.5wt% and 4.0 wt%, respectively, followed by steam treatment at 600 ℃ for 5 hours and oxalic acid acidification at 60 ℃ for 2hours and calcination at 540 ℃ for 2 hours, and the obtained catalyst was denoted as Cat-I.
Example 6
In comparative example 1, the binder-free product B was washed with distilled water, dried, calcined at 550 ℃ for 4 hours, exchanged with 0.8 mol/L ammonium nitrate solution at 80 ℃ for 3 times, washed with water for 2 times, dried at 120 ℃ and calcined at 540 ℃ for 3 hours to obtain an H-type molecular sieve, then the supported rare earth and aluminum were impregnated conventionally, dried at 85 ℃ for 2 hours and calcined at 550 ℃ for 4 hours using lanthanum nitrate and aluminum nitrate solutions, and the obtained supported amounts of La and Al were 2.5wt% and 4.0 wt%, respectively, followed by steam treatment at 600 ℃ for 5 hours and oxalic acid acidification at 80 ℃ for 2hours and calcination at 540 ℃ for 2 hours, and the obtained catalyst was denoted as Cat-J.
Comparative examples 1 to 4 and examples 1 to 6 reaction evaluation
The catalysts obtained in comparative examples 1 to 4 and examples 1 to 6 were respectively placed in a fixed bed reactor with an inner diameter of 12 mm and flowing continuously for evaluation of catalyst performance, the loading amount of the catalyst was 1 g, and the catalyst was loaded in N2Heating to 500 ℃ in the atmosphere for activation for 1 h, and then activating in N2The atmosphere is lowered to the reaction temperature, the feedstock is a carbon tetraliquefied gas (carbon tetraolefm: alkane: other =47: 0.1 The weight space velocity of the four-carbon liquefied gas is 10 h at the temperature of 530-580 ℃ under MPa-1. And cooling the product after reaction by a cooler for gas-liquid separation. The gas and liquid products were analyzed by an Agilent 7890A chromatography system for composition, the liquid product was Al2O3-S capillary column, hydrogen flame detector. The results of the analysis were normalized to give methane, ethane, propane, butane, ethylene, propylene, butene and C5 +And (4) product composition. Percentage used in the inventionAll are in weight percentage.
As shown in FIG. 1, the reaction results show that when the selectivity of dry gas on the catalyst is less than 3%, and the selectivity of ethylene + propylene in the product is not less than 64% (if the selectivity is not reached, the temperature is raised), the stability of the catalysts Cat-A, cat-B and Cat-C is not ideal, while the stability of the Cat-D catalyst is better than that of the catalysts Cat-A, cat-B and Cat-C, the stability of the catalysts Cat-E, cat-F and Cat-G is better than that of the catalysts Cat-D, and the stability of the catalysts Cat-H, cat-I and Cat-J is optimal.
The above-described embodiments are only some of the preferred embodiments and are not intended to limit the present invention. The invention may be practiced otherwise than as specifically described in this summary, and the scope of the invention is accordingly determined by the appended claims.
Claims (9)
1. The application of the binder-free ZSM-11 molecular sieve catalyst is characterized in that: the binder-free ZSM-11 molecular sieve catalyst is used for catalyzing and converting carbon four-olefin to generate ethylene and propylene, and the modification method of the binder-free ZSM-11 molecular sieve catalyst comprises the following steps:
(1) Burning off template agent of the prepared no-binder ZSM-11 molecular sieve catalyst, exchanging with ammonium nitrate solution, drying and roasting to prepare H-ZSM-11 molecular sieve catalyst;
(2) Loading rare earth and aluminum on the product obtained in the step (1) by a conventional impregnation method to obtain rare earth-AlZSM-11, and then drying and roasting in an air atmosphere;
(3) Treating, acidifying and roasting the product obtained in the step (2) in a steam atmosphere to obtain a modified binder-free ZSM-11 molecular sieve catalyst; the acidification temperature is 60 to 80 ℃, and the acidification time is 2 hours.
2. The use of the binder-free ZSM-11 molecular sieve catalyst of claim 1, wherein: in the step (3), acidification is realized by oxalic acid.
3. The use of the binderless ZSM-11 molecular sieve catalyst of claim 1, wherein: in the step (1), the concentration of the ammonium nitrate solution is 0.6-0.8 mol/L; the temperature of the exchange is 60-80 ℃.
4. The use of the binderless ZSM-11 molecular sieve catalyst of claim 1, wherein: in the step (1), the roasting temperature is 550-750 ℃, and the roasting time is 3-15 h.
5. The use of the binderless ZSM-11 molecular sieve catalyst of claim 1, wherein: in the rare earth-AlZSM-11 in the step (2), the load capacity of the rare earth is 0.1-6.0 wt%, and the load capacity of the aluminum is 0.5-5.0 wt%.
6. Use of the binderless ZSM-11 molecular sieve catalyst of claim 5, wherein: the loading amount of the rare earth is 1.0-3.0 wt%.
7. The use of the binder-free ZSM-11 molecular sieve catalyst of claim 1, wherein: in the step (2), the drying temperature is 80-100 ℃, and the drying time is 1-3 h; the roasting temperature is 550-700 ℃, and the roasting time is 3-6 h.
8. The use of the binderless ZSM-11 molecular sieve catalyst of claim 1, wherein: in the step (3), the water vapor treatment temperature is 550-750 ℃, and the time is 1-8 h.
9. The use of the binderless ZSM-11 molecular sieve catalyst of claim 8, wherein: in the step (3), the water vapor treatment time is 3-5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911238292.1A CN110975928B (en) | 2019-12-06 | 2019-12-06 | Modification method and application of binder-free ZSM-11 molecular sieve catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911238292.1A CN110975928B (en) | 2019-12-06 | 2019-12-06 | Modification method and application of binder-free ZSM-11 molecular sieve catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110975928A CN110975928A (en) | 2020-04-10 |
| CN110975928B true CN110975928B (en) | 2022-11-01 |
Family
ID=70090583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911238292.1A Active CN110975928B (en) | 2019-12-06 | 2019-12-06 | Modification method and application of binder-free ZSM-11 molecular sieve catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110975928B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111437879B (en) * | 2020-04-29 | 2023-03-10 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing methyl acrylate from methyl formate and acetylene |
| CN112246274A (en) * | 2020-10-19 | 2021-01-22 | 大连理工大学 | Preparation method of binder-free multi-stage pore ZSM-5 molecular sieve catalyst |
| CN115228506B (en) * | 2021-04-22 | 2023-09-26 | 中国科学院大连化学物理研究所 | ZSM-11 catalyst for preparing ethylene and propylene by C4 olefin pyrolysis and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11180902A (en) * | 1997-12-16 | 1999-07-06 | Agency Of Ind Science & Technol | Production of lower olefin |
| JP2005060355A (en) * | 2003-08-20 | 2005-03-10 | Idemitsu Petrochem Co Ltd | Method for producing olefin |
| CN1600757A (en) * | 2003-09-25 | 2005-03-30 | 中国科学院大连化学物理研究所 | Method for preparing propylene/ethane from catalytic cracking C4-C6 |
| WO2005105710A1 (en) * | 2004-04-30 | 2005-11-10 | Maruzen Petrochemical Company Limited | Method for producing lower olefin |
| CN1704387A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Catalyst for olefin cracking preparation of propylene and ethylene |
| CN101147874A (en) * | 2007-11-06 | 2008-03-26 | 东南大学 | Catalyst for preparing propylene and ethylene by C4 olefins and preparation method |
| CN102302945A (en) * | 2011-10-04 | 2012-01-04 | 大连理工大学 | Method for preparing propene by catalytic cracking |
| CN106673937A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method of preparing propylene by catalytic cracking of n-butene |
| CN107398294A (en) * | 2016-05-18 | 2017-11-28 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of the molecular sieve catalyst of modified no-adhesive ZSM-5-11 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156555C (en) * | 2000-08-10 | 2004-07-07 | 中国石油化工集团公司 | Assistant for calalytic cracking and its preparing process |
| JP4112943B2 (en) * | 2002-10-28 | 2008-07-02 | 出光興産株式会社 | Process for producing olefins by catalytic cracking of hydrocarbons |
| CN100443453C (en) * | 2005-09-07 | 2008-12-17 | 中国石油化工股份有限公司 | Method of preparing propylene and ethylene by catalytic cracking olefin |
| CN101279287B (en) * | 2007-04-04 | 2011-07-13 | 中国石油化工股份有限公司 | Catalyst for producing olefin hydrocarbon by catalytic pyrolysis |
| JP5288255B2 (en) * | 2008-10-29 | 2013-09-11 | 独立行政法人産業技術総合研究所 | Catalyst for producing lower olefin, process for producing the same, and process for producing lower olefin using the same |
-
2019
- 2019-12-06 CN CN201911238292.1A patent/CN110975928B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11180902A (en) * | 1997-12-16 | 1999-07-06 | Agency Of Ind Science & Technol | Production of lower olefin |
| JP2005060355A (en) * | 2003-08-20 | 2005-03-10 | Idemitsu Petrochem Co Ltd | Method for producing olefin |
| CN1600757A (en) * | 2003-09-25 | 2005-03-30 | 中国科学院大连化学物理研究所 | Method for preparing propylene/ethane from catalytic cracking C4-C6 |
| WO2005105710A1 (en) * | 2004-04-30 | 2005-11-10 | Maruzen Petrochemical Company Limited | Method for producing lower olefin |
| CN1704387A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Catalyst for olefin cracking preparation of propylene and ethylene |
| CN101147874A (en) * | 2007-11-06 | 2008-03-26 | 东南大学 | Catalyst for preparing propylene and ethylene by C4 olefins and preparation method |
| CN102302945A (en) * | 2011-10-04 | 2012-01-04 | 大连理工大学 | Method for preparing propene by catalytic cracking |
| CN106673937A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method of preparing propylene by catalytic cracking of n-butene |
| CN107398294A (en) * | 2016-05-18 | 2017-11-28 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of the molecular sieve catalyst of modified no-adhesive ZSM-5-11 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110975928A (en) | 2020-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110975928B (en) | Modification method and application of binder-free ZSM-11 molecular sieve catalyst | |
| US9242236B2 (en) | Catalytic composition for producing olefins by catalytic cracking | |
| CN100391610C (en) | Catalytic cracking fluid bed catalyst containing molecular sieve | |
| US20110124939A1 (en) | Dehydration of Alcohols on Crystalline Silicates | |
| EA019181B1 (en) | Dehydration of alcohols in the presence of an inert component | |
| US9480975B2 (en) | Catalyst for catalytic cracking in a fluidized bed | |
| JP2007125515A (en) | Catalyst for liquefied petroleum-gas production and production method of liquefied petroleum-gas using it | |
| CN109890503A (en) | Using modified crystalline aluminosilicate to monohydric alcohol dehydrating process | |
| Cheng et al. | Methanol promoted naphtha catalytic pyrolysis to light olefins on Zn-modified high-silicon HZSM-5 zeolite catalysts | |
| US7432410B2 (en) | Production of LPG containing propane or butane from dimethyl ether or methanol | |
| CN107398294B (en) | Preparation method and application of modified binder-free ZSM-11 molecular sieve catalyst | |
| CN111589467A (en) | Preparation and application of hollow ZSM-5 molecular sieve catalyst | |
| KR101386291B1 (en) | Ｚｓｍ-5 catalyst with micropores and mesopores, preparation method thereof and production method of light olefins through catalytic cracking of hydrocarbons using the catalyst | |
| JP5288255B2 (en) | Catalyst for producing lower olefin, process for producing the same, and process for producing lower olefin using the same | |
| JP2010042344A (en) | Catalyst for manufacturing lower olefin, method of manufacturing the same and method of manufacturing lower olefin using catalyst | |
| US20070170093A1 (en) | Hydrocarbon cracking catalyst and method for preparing the same | |
| WO2015152159A1 (en) | Method for producing unsaturated hydrocarbon | |
| JP2010042343A (en) | Catalyst for manufacturing lower olefin, method of manufacturing the same and method of manufacturing lower olefin using catalyst | |
| CN113385223A (en) | Catalyst for directly catalytically cracking crude oil to increase yield of low-carbon olefin and preparation method thereof | |
| Abdillahi et al. | Barium modification of a high-silica zeolite for methanol conversion to light alkenes | |
| CN115228506B (en) | ZSM-11 catalyst for preparing ethylene and propylene by C4 olefin pyrolysis and preparation method thereof | |
| JP2022549727A (en) | Catalyst for producing isopropylbenzene and its production method and use | |
| US20220008900A1 (en) | Nickel-Based Oligomerization Catalysts and Method for Oligomerizing Light Olefins Using the Same | |
| JP5288256B2 (en) | Catalyst for producing lower olefin, process for producing the same, and process for producing lower olefin using the same | |
| Cañizares et al. | Comparative study of the catalytic properties of ferrierite zeolite exchanged with alkaline earth metals in the skeletal isomerization of n-butene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |